Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/906—Polysulfone

Definitions

• the present invention relates to high temperature resistant polysulfone-polyimide block copolycondensates formed from selected polyarylene ether sulfone blocks and specific polyimide blocks and prepared by polycondensation of the polyimide blocks in the melt.
• Polyarylene ether sulfones have good mechanical properties, for example toughness and heat aging resistance, and also good electrical properties.
• Random ether sulfone/ether ketone copolymers composed of repeat units ##STR3## are described for example in EP-A-1879 These polycondensates are obtainable by simultaneous condensation of hydroquinone, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenyl sulfone.
• arylene ether ketone polycondensates containing bridge members such as --CO--, --SO--, --S--, --SO 2 --, --O--, alkylene, cycloalkylene, arylene, alkylidene or cycloalkylidene of from 2 to 20 carbon atoms are known, for example from EP-A-030,033 or EP-A-161,453.
• Polyimides are also known A comprehensive review of their preparation, properties and use is given for example in the monograph, Polyimides, Volumes 1 and 2, edited by K. L. Mittal and published by Plenum Press, New York and London, 1971, and in Chemical Process Review No. 54, Polyimide Manufacture, 1971, by Dr. M. W. Ranney, Noyes Data Corporation, New Jersey.
• polyarylene ether sulfones To prepare polyarylene ether sulfones, the aromatic dichloro and dihydroxy compounds are polycondensed in polar aprotic solvents in the presence of alkali metal carbonates and the products are then isolated by separating off the solvent or by precipitating with nonsolvents.
• Polyimides are likewise polycondensed in polar aprotic solvents
• polyamidocarboxylic acids are prepared in a first reaction stage from aromatic tetracarboxylic dianhydrides and aromatic diamines and then dehydrated in a second reaction stage, usually in the presence of carboxylic anhydrides and tertiary amines as catalyst.
• the polycondensates should be inexpensive to produce by an industrially practicable process.
• the thermal cyclization of the polyamidocarboxylic acid intermediates to polyimides eliminates the need not only for the dehydrating treatment of the polyamidocarboxylic acids with carboxylic anhydrides in solution but also for the subsequent isolation of the polysulfone-polyimide block copolycondensates by precipitation with nonsolvents, filtration, washing and drying under reduced pressure.
• the incorporation of polyimide blocks into polyarylene ether sulfone block polycondensates reduces not only their solubility but also their stress crack susceptibility.
• the polyimide blocks also raise the glass transition temperature of the block copolycondensates, thereby distinctly improving the stability of the mechanical properties under a sustained load within the range from 160° to 180° C.
• the present invention accordingly provides a high temperature resistant polysulfone-polyimide block copolycondensate containing or preferably consisting of
• (A) from 70 to 98 mol %, preferably from 80 to 95 mol %, in particular from 85 to 95 mol %, based on the total amount of (A) and (B), of polyarylene ether sulfone blocks having a number average molecular weight Mn within the range from 1,500 to 20,000 and composed of units of the formulae ##STR4## or of mixtures of units of the formulae (I) and (II), bonded in random distribution or in the form of blocks, and
• (B) from 2 to 30 mol %, preferably from 5 to 20 mol %, in particular from 5 to 15 mol %, based on the total amount of (A) and (B), of polyimide blocks having a number average molecular weight Mn of from around 400 to 5,000 and composed of units of the formulae ##STR5## or of mixtures of units of the formulae (III) and (IV), where R 1 and R 2 are identical or different and each is methyl or preferably hydrogen and
• X is a bridge member from the group consisting of --CH 2 CH 2 -- and preferably --CH 2 --
• the present invention also provides a process for preparing a high temperature resistant polysulfonepolyimide block copolycondensate, which comprises
• the present invention further provides shaped articles containing or consisting of a high temperature resistant polysulfone-polyimide block copolycondensate as claimed in any one of claims 1 to 5.
• Component (A) of the polysulfone-polyimide block copolycondensates according to the present invention comprises, as mentioned, polyarylene ether sulfone blocks of units of the formulae (I) or (II) ##STR6##
• polyarylene ether sulfone blocks which consist of mixtures of the units of the formulae (I) and (II) and contain these units in random distribution or in the form of blocks
• the number average molecular weight M n of the polyarylene ether sulfone blocks (A) is within the range from 1,500 to 20,000, preferably from 3,000 to 19,000, in particular from 5,000 to 18,000.
• Component (B) of the high temperature resistant polysulfone-polyimide block copolycondensates according to the present invention comprises, again as mentioned, polyimide blocks composed of units of the formulae ##STR7## or mixtures of units of the formulae (III) or (IV), wherein the units can be arranged in random distribution or in block form and R 1 , R 2 and X are each as defined above.
• units of the formulae (III) and (IV) of the polyimide blocks are ##STR8## where D is ##STR9## Preference is given to units of the formulae ##STR10## and in particular to units of the formulae ##STR11## or mixtures of at least two units of the formulae (III1) to (III3) and (IV1) to (IV3), in particular mixtures of units of the formulae (III1) and (IV1).
• the number average molecular weight Mn of the polyamide blocks (b) is within the range from 400 to 5,000, preferably from 800 to 4,500 and in particular from 1,000 to 4,000.
• the high temperature resistant polysulfone-polyimide block copolycondensates according to the present invention can be prepared continuously or batchwise in a two-stage reaction.
• the polyarylene ether sulfone blocks (A) in particular those having terminal amino groups
• the polyimide blocks, in particular those having terminal anhydride groups can be separately prepared and subsequently joined together by art recognized methods, or the block copolycondensates are synthesized directly by appropriate successive addition of the monomers.
• aromatic dihalogen compounds, aromatic dihydroxy compounds and aromatic aminohydroxy compounds are polycondensed in polar aprotic solvents in the presence of alkali metal carbonates in such a way that
• a first reaction stage comprises a reaction of
• polyarylene ether sulfone block copolycondensates (A) with terminal amino groups are used in such amounts that the molar ratio of 4,4'-dihydroxydiphenyl sulfone and/or 2,2-(4,4'-dihydroxydiphenyl)propane:paraaminophenol and/or 2,2-(4-amino-4'-hydroxydiphenyl)propane is from 5:2 to 90:2, preferably from 50:2 to 75:2, and the ratio of chlorine atoms of 4,4'-dichlorodiphenyl sulfone:hydroxyl groups of the dihydroxy compounds and of p-aminophenol and/or 2,2-(4-amino-4'-hydroxydiphenyl)propane is within the range from 0.95:1 to 1.05:1, preferably 1:1.
• the resulting polyphenylene ether sulfone block polycondensates having terminal amino groups are reacted in a second reaction stage in the melt with cis,cis,cis,-cis-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride or mixtures of said dianhydrides and aromatic diamines selected from the group consisting of 3-methyl- or 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,2-(3-methyl- or 3,3'-dimethyl-4,4'-diaminodiphenyl)ethane, 1,2-(4,4'-diaminodiphenyl)ethane and preferably 4,4'-diaminodiphenylmethane or of mixtures of at least two of the aromatic diamines mentioned to form cocondensed polyimide blocks.
• the molar ratio of amine-terminated polyphenylene ether sulfone block polycondensates:aromatic diamines is from 1:1 to 1:15, preferably from 1:2 to 1:10.
• the cyclopentane- and/or 3,3',4,4'-benzophenone-tetracarboxylic dianhydride and the aromatic diamines and amine-terminated polyarylene ether sulfone block polycondensates are used in such amounts that the ratio of anhydride to amino groups is within the range from 0.95:1 to 1.05:1, preferably 1:1.
• the various polyarylene ether sulfone blocks and polyimide blocks can in principle be combined with one another in any desired manner as long as the preconditions of claim 1 are met.
• the total molecular weight of the polysulfonepolyimide block copolycondensates is within the range from 15,000 to 200,000, preferably from 15,000 to 100,000, in particular from 20,000 to 50,000.
• polyarylene ether sulfone blocks in particular the amine-terminated polyarylene ether sulfone polycondensates, are prepared under the same conditions, such as temperature, pressure, the solvent used and the presence or absence of additives (catalysts), as described for random copolycondensates in EP-A-113,112 and EP-A-135,130 and for amine-terminated copolycondensates in EP-A-107,897 and U.S. Pat. No. 4,540,748, so that no further details need be given here.
• the amount of N-methylpyrrolidone is in general from 5 to 100 moles, preferably from 5 to 20 moles, per mole of monomer. This produces a reaction solution solids content within the preferred range of from 5 to 50% by weight, particularly preferably from 10 to 40% by weight.
• the water formed in the course of the polycondensation can be removed by means of an azeotrope former, by applying reduced pressure or preferably by introducing a stream of nitrogen and distilling.
• Suitable azeotrope formers are all compounds which under atmospheric pressure boil within the range of the reaction temperature and are homogeneously miscible with the reaction mixture without entering into chemical reactions.
• the reaction temperature is in general within the range from 130° to 220° C., preferably from 160° to 210° C.; the reaction time is in general from 0.1 to 15 hours.
• the amine-terminated polyarylene ether sulfone block polycondensates can be isolated from the solution by evaporating the solvent or by precipitation with a suitable nonsolvent, for example water, an alkanol, etc.
• the amine-terminated polyarylene ether sulfone blocks, aromatic diamines and aromatic tetracarboxylic dianhydrides are preferably polycondensed in the melt, advantageously in the presence of an inert gas, e.g. a noble gas, carbon monoxide or preferably nitrogen, at from 300° to 350° C., preferably at from 340° to 350° C.
• an inert gas e.g. a noble gas, carbon monoxide or preferably nitrogen
• the polyamidocarboxylic acid intermediates formed are directly dehydrated to polyimide block polycondensates under the existing reaction conditions.
• the water of reaction formed is distilled off.
• the reaction time for the polycondensation of the polyimide blocks is customarily 5-30 minutes, preferably 10-20 minutes
• the separately prepared amine-terminated polyarylene ether sulfones, aromatic diamines and aromatic tetracarboxylic dianhydrides are mixed in customary mixing apparatus, for example mixers, at from 15° to 80° C., preferably at from 20° to 30° C., and then polycondensed in the melt in an extruder, preferably in a twin-screw extruder having devolatilizing means.
• the polysulfone-polyimide block copolycondensate melt formed is then extruded, cooled down and granulated.
• the granules obtained may be stored, modified or used directly for producing, for example, films, coatings or preferably shaped articles.
• the products are notable for improved solvent resistance, low stress crack susceptibility and mechanical stability under a sustained load, even at elevated temperature, for example 160° C. or higher.
• polysulfone-polyimide block copolycondensates prepared according to the present invention by melt condensation may be modified with reinforcing fillers, pigments and other auxiliaries and additives.
• Suitable reinforcing fillers are for example carbon and preferably glass fibers, the glass fibers being used for example in the form of glass weaves, mats, webs and/or preferably glass filament rovings or chopped glass filament made of low-alkali E-glasses from 5 to 20 ⁇ m, preferably 8 to 15 ⁇ m, in diameter, the average length following incorporation being from. 0.05 to 1 mm, preferably from 0.1 to 0.5 mm.
• the molding compositions reinforced with glass filament rovings or chopped glass filament contain from 10 to 60% by weight, preferably from 20 to 50% by weight, of the reinforcing agent, based on the total weight, while the impregnated glass weaves, mats and/or webs contain from 10 to 80% by weight, preferably from 30 to 60% by weight, of polysulfone-polyimide block copolycondensates, based on the total weight.
• Suitable pigments are for example titanium dioxide, cadmium oxide, zinc sulfide, barium sulfate and carbon black.
• Other possible additives and auxiliaries are for example dyes, lubricants, e.g.
• the high temperature resistant polysulfone-polyimide block copolycondensates according to the present invention are preferably used for producing shaped articles consisting partially or advantageously completely of the block copolycondensates.
• the reduced viscosity ⁇ n spec/c of the amine-terminated polyarylene ether sulfone block polycondensates was determined at 25° C. in 1% strength by weight solution in N-methylpyrrolidone and that of the polysulfone-polyimide block copolycondensates according to the present invention at 60° C. in 0.1% strength by weight solution in pentafluorophenol.
• the polysulfone block polycondensate was precipitated with 1:1 w/w water/methanol, washed four times with 3,000 ml of water each time, filtered off and dried under reduced pressure for 12 hours.
• the product obtained had a reduced viscosity in N-methylpyrrolidone of 0.26 dl/g and contained 82 5% of amino end groups, based on the number of end groups.
• Example 1 was repeated using the starting materials in the following amounts:
• the resulting polysulfone block polycondensate had a reduced viscosity in N-methylpyrrolidone of 0.38 dl/g and 71% of amino end groups, based on the total number of end groups.
• Example 1 was repeated, except that the following starting materials and amounts were used:
• the product obtained had a reduced viscosity in N-methylpyrrolidone of 0.28 dl/g and 84% of amino end groups, based on the total number of end groups.
• Example 1 was repeated using the starting materials in the following amounts:
• the resulting amine-terminated polyarylene ether sulfone block copolycondensate had a reduced viscosity in N-methylpyrrolidone of 0.23 dl/g and 72% of amino end groups, based on the total number of end groups.
• Example 1 was repeated using the following starting materials and amounts:
• the resulting amine-terminated polyarylene ether sulfone block copolycondensate had a reduced viscosity in N-methylpyrrolidone of 0.34 dl/g and 69% of amino end groups, based on the total number of end groups.
• the polysulfone-polyimide block copolycondensate prepared in this way had a reduced viscosity in pentafluorophenol of 0.58 dl/g and a glass transition temperature Tg of 192° C. (measured by DSC).
• Example 6 was repeated using the starting materials in the following amounts:
• the polysulfone-polyamide block copolycondensate obtained had a reduced viscosity in pentafluorophenol of 0.46 dl/g and a glass transition temperature Tg of 189° C. (measured by DSC).
• Example 6 was repeated using the following starting materials and amounts:
• the polysulfone-polyimide block copolycondensate obtained had a reduced viscosity in pentafluorophenol of 0.57 dl/g and a glass transition temperature Tg of 198° C. (measured by DSC).
• Example 6 was repeated using the following starting materials and amounts
• the polysulfone-polyimide block copolycondensate obtained had a reduced viscosity in pentafluorophenol of 0.60 dl/g and a glass transition temperature Tg of 195° C. (measured by DSC).
• Example 6 was repeated using the following starting materials and amounts:
• the polysulfone-polyimide block copolycondensate obtained had a reduced viscosity in pentafluorophenol of 0.56 dl/g and a glass transition temperature Tg of 191° C. (measured by DSC).
• Example 6 was repeated using the following starting materials and amounts:
• the polysulfone-polyimide block copolycondensate obtained had a reduced viscosity in pentafluorophenol of 0.45 dl/g and a glass transition temperature Tg of 223° C. (measured by DSC).

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 1989
  • 1989-01-12 DE DE3900675A patent/DE3900675A1/de not_active Withdrawn
  • 1989-12-15 US US07/451,233 patent/US5036146A/en not_active Expired - Fee Related
  • 1989-12-27 JP JP1336803A patent/JPH02215837A/ja active Pending
• 1990
  • 1990-01-04 EP EP19900100147 patent/EP0378105A3/de not_active Withdrawn

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